Metal organic framework compounds

ABSTRACT

The invention provides novel Zr MOFs, in particular compounds having a surface area of at least 1020 m 2 /g or if functionalized, having a surface area of at least 500 m 2 /g.

This invention relates to Zr-MOFs, to their production, to their use,and to compositions and devices containing them.

MOFs or “metal organic frameworks” are compounds having a latticestructure having vertices or “cornerstones” which are metal-basedinorganic groups, for example metal oxides, linked together by organiclinker groups. These compounds have been developed by, for example, OmarYaghi and co-workers, currently of the University of Michigan, and arepromising materials for many applications.

Thus for example MOFs have been proposed for gas storage, as catalystmaterials and so on.

Perhaps the best known MOF is MOF-5 in which each Zn₄O cornerstone iscoordinated by six bis-carboxylate organic linkers.

Other MOFs in which the inorganic cornerstone is for example chromium,copper, vanadium, cadmium and iron have been made.

The utility of the known MOFs however is limited by their thermal andchemical sensitivity.

WO 2007/118874 discloses Zr-MOFs wherein the organic linkers areterephthalic acid. The Zr-MOFs taught in this document however possess asurface area of at most 836 m²/g.

We have now surprisingly found that Zr-MOFs with excellent stability,porosity and surface areas may be made using cornerstones based on Zr.

Thus viewed from one aspect the invention provides a Zr-MOF having asurface area of at least 1020 m²/g, especially at least 1050 m²/g,particularly at least 1200 m²/g, for example up to 10000 m²/g,especially up to 5000 m²/g .

The Zr-MOFs of the invention particularly preferably have a cornerstonehaving at least 20 coordination sites for the organic linkers, e.g.20-36, especially preferably at least 24, 30 or 36, most especially 24.In this way at least 10, more preferably at least 12 bidentate ligandgroups of the organic linkers can bind to each cornerstone. Previouslythe highest known number of coordination sites has been 18 for a Cr-MOF(the zinc-based MOF-5 has 12 coordination sites).

Especially preferably the cornerstone is a Zr₆O₃₂ structure, which has24 coordination sites per cornerstone.

Thus viewed from a further aspect the invention provides a Zr-MOF theinorganic cornerstones of which have at least 20 coordination sites, andpreferably having a surface area of at least 1020 m²/g, especially atleast 1050 m²/g, particularly at least 1200 m²/g, for example up to 5000m²/g, etc as above.

Viewed from a still further aspect the invention provides a Zr-MOFcomprising Zr₆O₃₂ cornerstones, and preferably having a surface area ofat least 1020 m²/g, etc as above.

Viewed from another aspect the invention provides a Zr-MOF having a Zrmetal atom to organic linker molecule ratio of from 1:0.45 to 1:0.55,especially 1:0.49 to 1:0.51, particularly 1:0.5, and preferably having asurface area of at least 1020 m²/g, etc as above.

Other preferred Zr metal atom to organic linker molecule ratios areabout 0.5:1, about 1:1, about 3:1 and about 1:3.

One especial advantage of such high numbers of coordination sites isthat functionalisation of the organic linkers may be effected, e.g. tocarry catalytic sites, without seriously weakening the MOF structure.

Viewed from another aspect the invention provides a functionalisedZr-MOF having a surface area of at least 500 m²/g, especially at least600 m²/g, especially at least 700 m²/g, particularly at least 1020 m²/getc as described above for unfunctionalised Zr-MOFs.

By functionalised MOF is meant a MOF, wherein one or more of thebackbone atoms of the organic linkers thereof carries a pendantfunctional group or itself forms a functional group. Functional groupsare typically groups capable of reacting with compounds entering the MOFor acting as catalytic sites for reaction of compounds entering the MOF.Suitable functional groups will be apparent to a person skilled in theart and in preferred embodiments of the invention include amino, thiol,oxyacid, halo and cyano groups or heterocyclic groups (e.g. pyridine),each optionally linked by a linker group, e.g. C₁₋₆, preferablycarbonyl. The functional group may also be a phosphorus-orsulfur-containing acid.

If an acid functional group possesses more than one labile hydrogen,then one or more of said labile hydrogens may itself be substitutedleaving one labile hydrogen.

If desired, a precursor to the functional group can be prepared, forexample an ether or ester group, or their phosphorous or sulfurequivalents.

The functionalised or unfunctionalised MOFs of the invention willpreferably have the cornerstones and/or Zr metal atom to organic linkermolecule ratios referred to above.

The new Zr-MOFs of the invention, besides having very high surfaceareas, and thus the ability to adsorb large volumes of gas, have bothhigh thermal and chemical stability, especially water stability.Moreover because of the nature of Group 4 metals, the Zr metal can be inmore than one oxidation state. This makes the Zr-MOFs of the inventionideal candidates for use as catalysts (e.g. in olefin polymerization),or more especially as electrodes in lithium batteries. The chemicalstability, in particular stability to exposure to water, a property rarein conventional MoFs, extends the range of possible applications, e.g.to include use in sustained release pharmaceutical formulations. Thethermal stability makes the Zr-MOFs of the invention particularly suitedfor gas storage since gas release is generally effected by raising thetemperature of the MOF.

We have also surprisingly found that Zr produces MOFs in which thestructure is porous and three-dimensional and does not comprise two ormore interpenetrating MOF structures, and so as a result the pore volumeis large and the structure open. This makes these MOFs particularlysuitable for most applications.

In conventional lithium batteries, e.g. lithium ion or lithium polymerbatteries, a graphite electrode is used. Repeated charging of thebatteries results in collapse of the graphite and as a consequence inshorter battery life. The Zr-MOFs of the invention have a strong andstable 3D structure and a wide range of possible oxidation states for Zrmaking them especially suitable for use in place of graphite as theelectrode material.

Thus viewed from a further aspect the invention provides the use of aZr-MOF as an electrode material in a lithium battery. Viewed from afurther aspect the invention provides a lithium battery having therein aZr-MOF as electrode material.

The lithium batteries according to the invention may produced simply bysubstituting the Zr-MOF for the graphite in a conventional lithiumbattery.

The Zr-MOFs of the invention are also particularly suitable forcontaining gases due to their very high surface area and stability. Thetypes of gases of interest are principally fuel gases such as hydrogen,methane and acetylene; however other gases may be adsorbed and, underraised temperature or reduced pressure, desorbed—thus they can also beused to capture gaseous contaminants or to hold other gases such as forexample nitrogen, carbon monoxide or carbon dioxide. Accordingly, viewedfrom a further aspect, the invention provides the use of a Zr-MOF toretain a gas, preferably hydrogen, methane or acetylene. Viewed from afurther aspect the invention provides a gas container, e.g. a fuel tankfor a motor vehicle, comprising a sealable vessel containing a Zr-MOF,optionally containing a gas, preferably hydrogen, methane or acetylene.Viewed from a further aspect the invention provides a hydrogen fuel cellhaving a hydrogen reservoir containing a Zr-MOF. Once again such devicesmay be constructed in conventional fashion.

Unlike most MOFs, we have found Zr-MOFs to be water- and acid-stable.They can therefore be used as drug reservoirs for pharmaceuticals foradministration into the gastrointestinal tract or for depot placementsubcutaneously whereby to achieve a sustained release of the drug.Sustained release allows the effect of the drug to continue longer andso allows less fragment administration. Thus viewed from a furtheraspect the invention provides physiologically tolerable Zr-MOFs for usein medicine. Viewed from another aspect the invention provides the useof a physiologically tolerable Zr-MOF for the manufacture of a sustainedrelease medicament for use in a method of treatment of a human ornon-human animal. Viewed from another aspect the invention provides asustained release pharmaceutical composition comprising aphysiologically tolerable Zr-MOF containing a drug substance, e.g. asubstance with therapeutic or prophylactic effect or with utility indiagnosis. Viewed from a still further aspect the invention provides amethod of treatment of a human or non-human animal subject whichcomprises administering an effective amount of a drug substance to saidsubject, the improvement comprising administering said substancecontained at least in part within a physiologically tolerable Zr-MOF.Administration will generally be oral, rectal, vaginal or viasubcutaneous depot placement, preferably oral. The drug substance may beany drug substance for which sustained release is desirable, e.g. ananti-infective, anti-inflammatory or anticancer agent, etc. Uptake ofthe drug substance by the MOF will generally be by contacting the MOFwith a solution, e.g. an aqueous solution, of the drug substance.

Biodegradation of the MOF will either not occur with the MOF beingexcreted intact or will generally release the organic linkers and theinorganic cornerstones. The cornerstones will generally be excretedintact and physiologically tolerable organic linkers may be selectedwith ease for MOF production. The drug loaded MOFs may be tabletted,encapsulated, put into dispersion or otherwise simply formulated intothe dosage forms for administration using conventional pharmaceuticaltechniques.

The Zr-MOFs may also be used as catalysts, either relying on thecatalytic activity of Zr, by using linkers with catalytic activity or byloading the MOF with a catalyst, e.g. a material which is simplyabsorbed into the MOF or which will bind to free functionalities on theorganic linkers in the MOF. Catalyst loading and subsequent reagentloading may be performed in conventional fashion. Thus viewed from afurther aspect the invention provides a catalyzed process for reacting areagent to produce a product, characterized in that as the catalyst orcatalyst carrier is used a Zr-MOF. Viewed from another aspect theinvention provides the use of a Zr-MOF as a catalyst or catalystsupport. Viewed from a still further aspect the invention provides aZr-MOF material having catalytic activity. Performance of catalyzedreactions within porous structures is known to allow great reactionspecificity and the Zr-MOFs may advantageously be used to this end.

The organic linkers of the Zr-MOFs of the invention may be any linkermolecule or molecule combination capable of binding to at least twoinorganic cornerstones and comprising an organic moiety. Thus the linkermay be any of the linkers conventionally used in MOF production (see forexample the publications by Omar Yaghi et al). These are generallycompounds with at least two cornerstone binding groups, e.g.carboxylates, optionally with extra functional groups which do not bindthe cornerstones but may bind metal ions on other materials it isdesired to load into the MOF. The introduction of such extrafunctionalities is straightforward as is described for example byCampbell in JACS 82:3126-3128 (1960). The linkers moreover typicallyhave rigidifying groups between the cornerstone-binding groups tofacilitate 3D MOF formation. Examples of suitable organic linkercompounds include oxalic acid, ethyloxalic acid, fumaric acid,1,3,5-benzene tribenzoic acid (BTB), DCPB, benzene tribiphenylcarboxylicacid (BBC), 5,15-bis (4-carboxyphenyl) zinc (II) porphyrin (BCPP),1,4-benzene dicarboxylic acid (BDC), 2-amino-1,4-benzene dicarboxylicacid (R₃-BDC or H₂N BDC), 1,1′-azo-diphenyl 4,4′-dicarboxylic acid,cyclobutyl-1,4-benzene dicarboxylic acid (R₆-BDC), benzene tricarboxylicacid, 2,6-naphthalene dicarboxylic acid (NDC), 1,1′-biphenyl4,4′-dicarboxylic acid (BPDC), 2,2′-bipyridyl-5,5′-dicarboxylic acid,adamantane tetracaboxylic acid (ATC), adamantane dibenzoic acid (ADB),adamantane teracarboxylic acid (ATC), dihydroxyterephthalic acid(DHBDC), biphenyltetracarboxylic acid (BPTC), tetrahydropyrene2,7-dicarboxylic acid (HPDC), hihydroxyterephthalic acid (DHBC), pyrene2,7-dicarboxylic acid (PDC), pyrazine dicarboxylic acid, acetylenedicarboxylic acid (ADC), camphor dicarboxylic acid, fumaric acid,benzene tetracarboxylic acid, 1,4-bis(4-carboxyphenyl)butadiyne,nicotinic acid, and terphenyl dicarboxylic acid (TPDC). Other acidsbesides carboxylic acids, e.g. boronic acids may also be used. A mixtureof linkers may be used to introduce functional groups within the porespace, e.g. by using aminobenzoic acid to provide free amine groups orby using a shorter linker such as oxalic acid. This introduction offunctionalised linkers is facilitated since the Zr-MOFs have excessinorganic cornerstone coordination sites beyond those required to formthe stable 3D MOF structure.

MOF construction is effected in solution, typically an organic solvent,for example DMF, using a soluble precursor Zr compound and the organiclinker and preferably in a molar ratio of from 0.6:1 to 3:1,particularly 0.8:1 to 2:1 especially about 1:1. The solution isgenerally heated, for example to 60 to 150° C., preferably 100 to 140°C., especially 110 to 130° C., particularly 115 to 125° C. (e.g. 80 to130° C. or 100 to 120° C.), and MOF formation is preferably allowed tooccur under static conditions, e.g. for up to 96 hours, especially 12 to72 hours, particularly 24 to 48 hours, (e.g. for 10 to 30 hours,especially 15 to 19 hours). The use of too long a formation period, e.g.7 days, or too high a formation temperature (e.g. at or above the upperlimits mentioned above) is generally undesirable as the surface area ofthe resulting MOF tends to be reduced. The Zr is preferably present inthe reaction solution at a concentration of 0.3-2.0 M, especially0.5-1.0 M, particularly 0.6-0.8 M. The reaction is preferably effectedunder an oxygen-free atmosphere and using water-free solvents. Theresulting MOF should then be washed with solvent (conveniently the oneused for the MOF formation reaction) and thoroughly dried. The surfacearea can be determined by use of nitrogen adsorption and the BET method.This method, by which the surface areas referred to herein may bedetermined, is described by Rouquerol et al in “Adsorption by powdersand porous solids”, Academic Press, San Diego, Calif., USA, 1999.

The solvent used is conveniently an alkanol, dimethyl formamide (DMF),toluene, methylethyl ketone, dimethylsulphoxide, tetrahydrofuran,cyclohexanone, diethyl formamide, N-methyl pyrridone, acetone, analkane, pyridine or acetonitrile. The use of DMF is especiallypreferred.

The Zr compound used is preferably a halide (e.g. the chloride), analcoholate or an acetonate. The metal may if desired be present in sucha reagent as an oxide cation.

The MOFs used as an electrode material in a lithium battery, or toretain a gas, or for use in a hydrogen fuel cell, or for use inmedicine, or used for the manufacture of a sustained release medicament,or for use as a catalyst carrier, catalyst support or catalyst, orhaving catalytic activity are preferably MOFs of the invention.

The invention will now be described further with reference to thefollowing non-limiting Examples and the accompanying drawings, in which:

FIG. 1 shows CuKα1 powder X-ray diffraction patterns of Zr-BDC MOF;

FIG. 2 is a CuKα1 powder X-ray diffraction pattern of Zr-BPDC MOF;

FIG. 3 is a simulated CuKα1 powder X-ray diffraction pattern of Zr-TPDCMOF also showing the observed diffraction peaks on the baseline;

FIG. 4 is a representation of the structure of Zr-BDC MOF; and

FIG. 5 is a representation of the structure of Zr-BPDC MOF;

FIG. 6 is a thermogravimetric curve for Zr-BDC MOF;

FIG. 7 shows BET nitrogen adsorption and desorption isotherms forZr-BDC. at 77° K;

FIG. 8 is the hydrogen adsorption isotherm for Zr-BDC. at 77° K; and

FIG. 9 is a representation of the structure of Zr-TPDC MOF.

FIG. 10 is a thermogravimetric curve for Zr-BDC MOF-NH₂ (B) compared tothat of Zr-BDC MOF (A) wherein curve (C) depicts the heat flow;

EXAMPLE 1 Zr-BDC MOF

Standard synthesis of Zr-BDC MOF was performed by dissolving ZrCl₄(0.053 g, 0.227 mmol, Aldrich) and 1,4-benzenedicarboxylic acid (H₂BDC)(0.034 g, 0.227 mmol, Aldrich) in N,N′-dimethylformamide (DMF) (24.9 g,340 mmol) at ambient temperature. The thus obtained mixture was sealedand placed in a pre-heated oven at 120° C. for 24 hours. Crystallizationwas carried out under static conditions. After cooling in air to ambienttemperature the resulting solid was filtered, repeatedly washed with DMFand dried at ambient temperature.

EXAMPLE 2 Zr-BPDC MOF

Standard synthesis of Zr-BPDC MOF was performed by dissolving ZrCl₄(0.0528 g, 0.230 mmol, Aldrich) and biphenyl-4,4-dicarboxylic acid(H₂BPDC) (0.055 g, 0.230 mmol, Aldrich) in N,N′-dimethylformamide (DMF)(24.9 g, 340 mmol) at ambient temperature. The thus obtained mixture wassealed and placed in a pre-heated oven at 120° C. for 24 hours.Crystallization was carried out under static conditions. After coolingin air to ambient temperature the resulting solid was filtered,repeatedly washed with DMF and dried at ambient temperature. The surfacearea is estimated to be in the region of 1800 m²/g.

EXAMPLE 3 Zr-TPDC MOF

Standard synthesis of Zr-TPDC MOF was performed by dissolving ZrCl₄(0.0528 g, 0.230 mmol, Aldrich) and terphenyl dicarboxylic acid (H₂TPDC)(0.072 g, 0.230 mmol, Aldrich) in N,N′-dimethylformamide (DMF) (24.9 g,340 mmol) at ambient temperature. The thus obtained mixture was sealedand placed in a pre-heated oven at 120° C. for 24 hours. Crystallizationwas carried out under static conditions. After cooling in air to ambienttemperature the resulting solid was filtered, repeatedly washed with DMFand dried at ambient temperature. The surface area is estimated to be inthe region of 4000 m²/g.

EXAMPLE 4 Powder X-Ray Diffraction Patterns

Powder XRD patterns of the Zr-MOFs of Examples 1 to 3 were obtained withSiemens Bruker AXS D-5000 instruments using CuK-alpha-1 radiation inBragg-Brentano reflecting and Debye-Scherrer transmission geometry. Thesamples were thoroughly ground and transferred into 0.5 mm quartzcapillaries or deposited on glass plates. Powder patterns of desolvatedsamples were recorded after heating the samples to 300° C. for 60minutes, and sealing the capillaries before cooling to ambienttemperature. The patterns for the desolvated samples were used to solvethe crystal structures.

A temperature resolved series of powder XRD patterns was recorded with aSiemens D500 diffractometer using Cu radiation. The instrument wasequipped with beta-filter and Scintillator counter. Powder XRD patternswere collected in the temperature range 25-450° C. in steps of 25° C.and in nitrogen flow.

The powder X-ray diffraction patterns for as-synthesised and desolvatedZr-BDC MOF (Example 1) are shown in FIG. 1. The upper trace is thedesolvated Zr-BDC MOF, the lower the Zr-BDC MOF as synthesised. Arepresentation of the structure calculated for Zr-BDC MOF is shown inFIG. 4.

The powder X-ray diffraction pattern for as synthesised Zr-BPDC MOF(Example 2) is shown in FIG. 2. A representation of the structurecalculated for Zr-BPDC MOF is shown in FIG. 5.

The simulated powder X-ray diffraction pattern for as synthesisedZr-TPDC MOF (Example 3) is shown in FIG. 3 with the observed peaks shownon the baseline. A representation of the structure calculated forZr-TPDC MOF is shown in FIG. 9.

EXAMPLE 5 Thermogravimetric Analysis and Temperature ProgrammedAdsorption/Desorption

Thermogravimetric (TG) analysis and temperature programmedadsorption/desorption (TPA/TPD) were carried out in flowing nitrogenatmosphere (15 mL/min) using a Rheometric Scientific STA 1500instrument. The TG analyses were performed parallel with on-line massspectrometric (MS) analysis. The MS data were recorded with PfeifferOmniStar GDS 300 O quadrupole equipped with an electron multiplierdetector. The approximate sample weight was 10 mg in all experiments andthe heating rate in TG experiment was 5 C°/min. In the TPA/TPDexperiments, the solvent molecules in the structure were removed byheating the sample to 300° C. (heating rate 10 C°/min). The sample wasthan cooled to 25° C. and carrier gas (nitrogen) saturated with probemolecules (water and DMF) was admitted to the sample. After weightstabilization, the sample was reheated again to 300° C.

The adsorption of nitrogen was measured volumetrically with aBELSORP-mini II instrument and the specific surface area was obtained bythe BET method. The sample was heated to 250° C. and kept at thistemperature under continuous evacuation for 6 hours prior to adsorptionmeasurement. The hydrogen, methane, and carbon dioxide adsorptionisotherms were recorded on an Autosorb Quanta Chrome instrument afterpretreating of sample at 250° C. for 1 hour.

The thermographic curve recorded for Zr-BDC MOF (Example 1) is shown inFIG. 6. As can be seen, the material is stable up to about 500° C.

The recorded nitrogen adsorption/desorption plot for Zr-BDC MOF at 77° Kis shown in FIG. 7. Solid squares and open squares are respectively datapoints for adsorption and desorption. The adsorption of nitrogen followsa type I isotherm with no hysteresis, and with a BET surface area of1069 m²/g (corresponding to a Langmuir surface area of 1191.5 m²/g).

The recorded hydrogen adsorption isotherm for Zr-BDC MOF at 77° K isshown in FIG. 8. The hydrogen storage capacity is 1.2 wt % at standardtemperature and pressure (STP).

EXAMPLE 6 Zr-carborane MOF

a) Preparation of 1,12-Dihydroxycarbonyl-1,12-dicarba-closo-dodecaborane

1,12-Dihydroxycarbonyl-1,12-dicarba-closo-dodecaborane was synthesisedby the method of Hubbs, i.e. by adding 1.6M (35 mL, 56 mmol) n-BuLi viasyringe to 2 g (13.9 mmoles) of 1,12-dicarba-closododecaborane(p-carborane), dissolved in 150 mL of dry diethyl ether and stirred at0° C. The reaction mixture was warmed to ambient temperature and thenrefluxed for 1.5 hours. The reaction was then cooled to −78° C.utilizing a dry-ice/acetone bath. Carbon dioxide gas was bubbled intothe reaction mixture for an hour while stirring. Diethyl ether wasconcentrated and the white solid was stirred in 100 mL of 3Mhydrochloric acid.

The thus obtained precipitate was filtered and washed in the followingorder: chilled water, hexane, chloroform. The title product was obtainedas white solid (2.81 g, 87%) and dried under vacuum overnight.

b) Preparation of Zr-carborane MOF

ZrCl₄ (0.027 g, 0.11 mmol, Aldrich), Zn(NO₃)·6H₂O (33 mg, 0.11 mmol) and1,12-dicarboxylic-1,12-dicarba-closo-dodecaborane (8.3 mg, 0.035 mmol)were dissolved in a vial in 1 ml of dimethylformamide. The solution washeated at 100° C. for 24 hours to yield the Zr-carborane MOF.

EXAMPLE 7 Zr-BDC MOF-NH₂

To further expand the scope of use for the Zr-MOFs we have nowincorporated an amine group into the structure by the use of2-aminoterephthalic acid during synthesis, thereby synthesising the MOFZr-BDC MOF-NH₂ with the same morphology as Zr-BDC MOF.

The solvent interaction is stronger in this functionalized MOF. DMF mustbe exchanged with ethanol or methanol before evacuation in order toobserve a surface area that is close to the calculated value of 900m²/g.

Standard synthesis of Zr-BDC MOF-NH₂ was performed by dissolving ZrCl₄(0.053 g, 0.227 mmol, Aldrich) and 2-aminoterephthalic acid (0.041 g,0.227 mmol, Aldrich) in N,N′- dimethylformamide (DMF) (24.9 g, 340 mmol)at ambient temperature. The thus obtained mixture was sealed and placedin a pre-heated oven at 120° C. for 24 hours. Crystallization wascarried out under static conditions. After cooling in air to ambienttemperature the resulting solid was filtered, repeatedly washed with DMFand dried at ambient temperature.

EXAMPLE 8 Zr-bipyridine MOF

Standard synthesis of Zr-dipyridine MOF was performed by dissolvingZrCl₄ (0.047 g, 0.22 mmol, Aldrich) and 2,2′-bipyridine-5,5-dicarboxylicacid (0.0488 g, 0.227 mmol, Aldrich) in N,N′-dimethylformamide (DMF)(24.9 g, 340 mmol) at ambient temperature. The thus obtained mixture wassealed and placed in a pre-heated oven at 100° C. for 48 hours.Crystallization was carried out under static conditions. After coolingin air to ambient temperature the resulting solid was filtered,repeatedly washed with DMF and dried at ambient temperature

EXAMPLE 9 Zr-bipyridine-Pt MOF

Standard synthesis of Zr-dipyridine-Pt MOF was performed by dissolvingZrCl₄ (0.047 g, 0.22 mmol, Aldrich) and 2,2′-bipyridine-5,5-dicarboxylicacid (0.0488 g, 0.227 mmol, Aldrich) and K₂PtCl₆ (99.6 mg) inN,N′-dimethylformamide (DMF) (24.9 g, 340 mmol) at ambient temperature.The thus obtained mixture was sealed and placed in a pre-heated oven at100° C. for 48 hours. Crystallization was carried out under staticconditions. After cooling in air to ambient temperature the resultingsolid was filtered, repeatedly washed with DMF and dried at ambienttemperature.

1. A Zr-MOF having a surface area of at least 1020 mVg.
 2. Afunctionalised Zr-MOF having a surface area of at least 500 mVg.
 3. AZr-MOF the inorganic cornerstones of which have at least 20 coordinationsites.
 4. A Zr-MOF comprising Zr₆O₃₂ cornerstones.
 5. A Zr-MOF having aZr metal atom to organic linker molecule ratio of from 1:0.45 to 1:0.55.6-11. (canceled)
 12. Physiologically tolerable Zr-MOFs for use inmedicine.
 13. The use of a physiologically tolerable Zr-MOF for themanufacture of a sustained release medicament for use in a method oftreatment of a human or non-human animal.
 14. A sustained releasepharmaceutical composition comprising a physiologically tolerable Zr-MOFcontaining a drug substance, e.g. a substance with therapeutic orprophylactic effect or with utility in diagnosis.
 15. A method oftreatment of a human or non-human animal subject which comprisesadministering an effective amount of a drug substance to said subject,the improvement comprising administering said substance contained atleast in part within a physiologically tolerable Zr-MOF.
 16. A catalyzedprocess for reacting a reagent to produce a product, characterized inthat as the catalyst or catalyst carrier is used a Zr-MOF.
 17. The useof a Zr-MOF as a catalyst or catalyst support .
 18. A Zr-MOF materialhaving catalytic activity.
 19. The Zr-MOF as claimed in claim 2 havingthe inorganic cornerstones of which have at least 20 coordination sites.20. A Zr-MOF as claimed in claim 2 having a Zr metal atom to organiclinker molecule ratio of from 1:0.45 to 1:0.55.
 21. A Zr-MOF as claimedin claim 3 having a Zr metal atom to organic linker molecule ratio offrom 1:0.45 to 1:0.55.